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GaAs layers have been grown on porous silicon (PS) substrates with good crystallinity by molecular beam epitaxy. In spite of the surface irregularity of PS substrates, no surface morphology deterioration was observed on epitaxial GaAs overlayers. A 10% Rutherford backscattering spectroscopy minimum channeling yield for GaAs‐on‐PS layers as compared to 16% for GaAs‐on‐Si layers grown under the same condition indicates a possible improvement of crystallinity when GaAs is grown on PS. Transmission electron microscopy reveals that the dominant defects in the GaAs‐on‐PS layers are microtwins and stacking faults, which originate from the GaAs/PS interface. GaAs is found to penetrate into the PS layers. n‐type GaAs/p‐type PS heterojunction diodes were fabricated with good rectifying characteristics.